Hole delocalization in oxidized cerium(IV) porphyrin sandwich complexes
Optical absorption, electron paramagnetic resonance, and resonance Raman spectra are reported for the one-electron oxidation products of the Ce(IV) sandwich porphyrins, Ce(OEP)/sub 2/ and Ce(TPP)/sub 2/ (OEP = octaethylporphyrin; TPP = tetraphenylporphyrin). These data, in conjunction with electrochemical measurements, indicate that the holes of both oxidized species are delocalized on the vibrational and probably the electronic time scales. In Ce(OEP)/sub 2//sup +/, the hole is delocalized through purely porphyrin-porphyrin interactions. In Ce(TPP)/sub 2//sup +/, delocalization is further facilitated by participation of the f orbitals of the Ce(IV) ion. The different characteristics of the redox orbitals of Ce(OEP)/sub 2//sup +/ and Ce(TPP)/sub 2//sup +/ are accounted for by the fact that oxidation occurs from an a/sub lu/-like orbital in the former complex and from an a/sub 2u/-like orbital in the latter.
- Research Organization:
- Carnegie Mellon Univ., Pittsburgh, PA (USA)
- OSTI ID:
- 5837247
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:18; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Spectroscopic characterization of triple-decker lanthanide porphyrin sandwich complexes. Effects of strong. pi. pi. interactions in extended assemblies
Effects of steric and electronic interactions on. pi. pi. overlap in lanthanide porphyrin sandwich complexes
Related Subjects
140505 -- Solar Energy Conversion-- Photochemical
Photobiological
& Thermochemical Conversion-- (1980-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400400 -- Electrochemistry
ABSORPTION SPECTROSCOPY
CARBOXYLIC ACIDS
CERIUM COMPLEXES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
ELECTROCHEMISTRY
ELECTRON SPIN RESONANCE
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HOLES
INFORMATION
LASER SPECTROSCOPY
LAYERS
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
PORPHYRINS
RAMAN SPECTROSCOPY
RARE EARTH COMPLEXES
RESONANCE
SPECTROSCOPY